CN110872254B - Pyrazole salt diionic liquid and method for catalytic synthesis of cyclic carbonate by using same - Google Patents
Pyrazole salt diionic liquid and method for catalytic synthesis of cyclic carbonate by using same Download PDFInfo
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- CN110872254B CN110872254B CN201911164990.1A CN201911164990A CN110872254B CN 110872254 B CN110872254 B CN 110872254B CN 201911164990 A CN201911164990 A CN 201911164990A CN 110872254 B CN110872254 B CN 110872254B
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- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
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- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0298—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature the ionic liquids being characterised by the counter-anions
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C277/08—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups of substituted guanidines
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- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
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Abstract
The invention relates to a pyrazole salt diionic liquid, which has the following structure:
Description
Technical Field
The invention belongs to the technical field of environment-friendly catalysis, and particularly relates to a novel pyrazole salt diionic liquid and a method for synthesizing cyclic carbonate by cycloaddition reaction by using the novel ionic liquid as a catalyst.
Background
CO 2 As a main greenhouse gas, the green-house gas seriously influences the global environment and the social activities of human beings, but also is a cheap, rich, nontoxic and renewable C1 resource. CO 2 2 Not only can reduce CO in the atmosphere 2 The concentration of the (B) can provide sustainable supplement for limited fossil fuels, and chemical products with high added values can be obtained, which has great significance from the perspective of green sustainability. In a large number of CO 2 In the conversion utilization pathway, CO 2 The cycloaddition reaction with epoxy compounds is the most efficient and widely used process, on the one hand it is characterized by atom economy and negligible by-productsOn the other hand, the cyclic carbonate produced is widely used. The cyclic carbonate can be used as a polar aprotic solvent, an electrolyte for a fuel cell or a lithium ion battery due to its high boiling point, large dielectric constant, and large dipole moment. In addition, cyclic carbonates are also common intermediates for the synthesis of other compounds.
Since cyclic carbonates have important economic potential and broad application prospects, further improvements in catalyst performance are needed to improve yields and reduce costs. Various homogeneous and heterogeneous catalysts have been reported for CO 2 And epoxy compounds, including alkali metal salts, metal organic framework compounds, molecular sieves, and ionic liquids. Among them, ionic liquids stand out among many catalysts for their unique advantages, such as high thermal stability, low vapor pressure, non-flammability, etc. In recent decades, various ionic liquids have been developed, such as functionalized ionic liquids, dicationic ionic liquids, and bifunctional ionic liquids, but in the absence of metal promoters or organic solvents, general ionic liquids may still have one or more of the disadvantages of difficult synthesis, low catalytic activity, and harsh catalytic conditions. Therefore, it is necessary to search for a high-efficiency ionic liquid having a high catalytic activity under mild conditions.
Disclosure of Invention
The invention aims to solve the problems of harsh reaction conditions, difficult catalyst synthesis, low catalyst activity, insufficient environmental protection and the like in the method for synthesizing cyclic carbonate, and provides a novel pyrazole salt diionic liquid and a method for synthesizing the cyclic carbonate by cycloaddition reaction under mild conditions by using the novel ionic liquid as a catalyst.
In order to realize the purpose, the invention adopts the following technical scheme:
the pyrazole salt diionic liquid has the following structure:
wherein n =1 or 2,X is Cl or Br.
The invention provides a preparation method of the pyrazole salt diionic liquid, which comprises the following steps: under the condition of organic solvent, halogenated carboxyethyl pyrazole salt and 1,1,3,3-tetramethylguanidine are subjected to neutralization reaction under the normal temperature condition to obtain the halogenated carboxyethyl pyrazole.
Further preferably, the organic solvent is methanol; the halogenated carboxyethyl pyrazole salt is carboxymethyl ethyl pyrazole salt chloride, carboxymethyl ethyl pyrazole salt bromide or carboxymethyl ethyl pyrazole salt bromide.
Further preferably, the molar ratio of the halogenated carboxyethyl pyrazole salt to 1,1,3,3-tetramethylguanidine is 1: 1.
The invention also provides a method for synthesizing cyclic carbonate by using the pyrazole salt diionic liquid as a catalyst, which comprises the following steps:
adding the pyrazole salt diionic liquid and the epoxy compound into a reaction kettle according to the molar ratio of 2-35: 100, keeping the reaction kettle in a closed state, introducing carbon dioxide to the pressure of 0.1-0.5 MPa (preferably 0.1 MPa), carrying out cycloaddition reaction for 1-16 h at the constant temperature and the constant pressure under the condition of the temperature of 30-60 ℃, and carrying out post-treatment after the reaction is finished to obtain the cyclic carbonate.
Further preferably, a small amount of water is added into the reaction kettle, so that the reaction is facilitated.
Further, the epoxy compound has the structure
。
More preferably, the molar ratio of the pyrazole salt diionic liquid to the epoxy compound is 10: 100.
Further preferably, the temperature of the cycloaddition reaction is 50 to 60 ℃, and the time of the cycloaddition reaction is 6 to 12h.
The invention discovers that: when a small amount of water, a green solvent, is added to the reaction, the cycloaddition reaction is more facilitated and the amount of the cyclic carbonate obtained is also larger. Further preferably, the molar ratio of water to the epoxy compound is 25 to 150: 100.
The method for synthesizing the cyclic carbonate takes carbon dioxide and an epoxy compound as reactants and prepares the cyclic carbonate through cycloaddition reaction, and the used catalyst is a product of neutralization reaction, namely a novel pyrazolate diionic liquid. Compared with the prior art, the invention has the following beneficial effects:
1) The invention has the main characteristics and advantages that the selected catalyst is novel, the catalyst is a novel pyrazole salt diionic liquid with double anions and cations, which is synthesized by neutralization reaction, the synthesis steps are simple and easy to prepare, the raw material cost is low, the catalyst is green and environment-friendly, the catalytic activity is high, and the catalyst still has good activity after being repeatedly used for eight times, and the catalyst is an ideal catalyst;
2) The method can achieve higher cyclic carbonate yield of 90.2% under the mild (normal temperature and pressure) condition, and can effectively improve the cyclic carbonate yield when a small amount of water is added, wherein the highest yield can achieve 99.5%. The added water is a green solvent, and is less polluting to the environment compared with organic solvents. When the temperature was raised to 50 ℃, satisfactory yield of cyclic carbonate (99%) was achieved with only a small amount of ionic liquid catalyst. From the above, it can be seen that the process of the present invention has great industrial applicability and is desirable.
Drawings
FIG. 1 is the [ TMGH ] prepared in example 1 + ][ - O 2 MEPZ + ][Br - ]Nuclear magnetic resonance hydrogen spectrum of the catalyst;
FIG. 2 is the [ TMGH ] prepared in example 1 + ][ - O 2 MEPZ + ][Br - ]Nuclear magnetic resonance carbon spectrum of the catalyst; it can be seen from fig. 1 and 2 that the synthesized catalyst is the target catalyst.
Detailed Description
The synthesis method of the pyrazole salt diionic liquid catalyst used in the present invention is illustrated by the following examples, which are only for illustrating the present invention and are not intended to limit the present invention.
Example 1 preparation of a pyrazole salt diionic liquid
The structural formula of the pyrazole diionic liquid catalyst prepared in the embodiment is as follows:
wherein n =1,X is Br.
The preparation method of the pyrazole salt diionic liquid comprises the following specific steps: putting 10mmol of bromocarboxymethylethyl pyrazole salt (CMEPzBr) and 10mmol of 1, 3-Tetramethylguanidine (TMG) into a 50mL flask, adding 15mL of methanol serving as a solvent, performing neutralization reaction at normal temperature for 12h, removing methanol by rotary evaporation after the reaction is finished, washing for multiple times by ethyl acetate, and obtaining the diionic liquid [ TMGH ] after the ethyl acetate is removed by rotary evaporation + ][ - O 2 MEPZ + ][Br - ]See fig. 1 and 2.
With reference to the above method, [ TMGH ] was obtained by replacing carboxymethylethylpyrazole bromide (CMEPzBr) with carboxyethylpyrazole bromide (CEEPzBr) or carboxymethylethylpyrazole chloride (CMEPzCl) + ][ - O 2 EEPZ + ][Br - ]And [ TMGH ] + ][ - O 2 MEPZ + ][Cl - ](ii) a Corresponding to n n =2 in the structural formula of the catalyst, and X is Br; and n =1, X is Cl.
Example 2
A method for synthesizing cyclic carbonate by using pyrazole salt diionic liquid as a catalyst specifically comprises the following steps:
firstly, the autoclave was cleaned, and the [ TMGH ] in example 1 was taken + ][ - O 2 MEPZ + ][Br - ]Putting 1.25mmol of catalyst into a 50mL high-pressure reaction kettle, adding 5mmol of epoxy chloropropane into the high-pressure reaction kettle, keeping the sealed reaction kettle in a sealed state and slowly introducing CO into the reaction kettle 2 Gas counterThe air in the kettle is removed, and finally CO is removed 2 The pressure is stabilized at 0.1MPa, then the reaction is carried out for 12h at 30 ℃, after the reaction is finished, the product is quantitatively analyzed by gas chromatography, and the product 4-chloromethyl- [1,3 is obtained]The yield of the dioxolan-2-one is 90.2 percent, and the selectivity is more than 99 percent.
Example 3
The specific experimental process and detection method are the same as those in example 2, and the difference is only that the catalyst used is [ TMGH ] + ][ - O 2 EEPZ + ][Br - ]The product yield was found to be 91.7% with a selectivity > 99%.
Example 4
The specific experimental process and detection method are the same as example 2, and the difference is only that the catalyst used is [ TMGH ] + ][ - O 2 MEPZ + ][Cl - ]The product yield was found to be 55.8% with a selectivity > 99%.
Example 5
The specific experimental process and detection method are the same as example 2, except that the catalyst accounts for 5 mol% of the molar content of the epichlorohydrin, the measured product yield is 77.7%, and the selectivity is more than 99%.
Example 6
The specific experimental process and the detection method are the same as those in example 2, and only differ in that the molar content of the catalyst in the epichlorohydrin is 10 mol%, the measured product yield is 79.4%, and the selectivity is more than 99%.
Example 7
The specific experimental process and detection method are the same as example 2, except that the molar content of the catalyst in the epichlorohydrin is 15 mol%, the measured product yield is 82.6%, and the selectivity is more than 99%.
Example 8
The specific experimental process and the detection method are the same as those in example 2, and only differ in that the molar content of the catalyst in the epichlorohydrin is 20 mol%, the measured product yield is 86.4%, and the selectivity is more than 99%.
Example 9
The specific experimental process and the detection method are the same as those in example 2, and only differ in that the molar content of the catalyst in the epichlorohydrin is 30 mol%, the measured product yield is 91.9%, and the selectivity is more than 99%.
Example 10
The specific experimental process and the detection method are the same as those in example 2, and only differ in that the molar content of the catalyst in the epichlorohydrin is 35 mol%, the measured product yield is 92.2%, and the selectivity is more than 99%.
Example 11
The specific experimental process and detection method are the same as example 2, except that the reaction time is 6 h, the product yield is 76.6%, and the selectivity is more than 99%.
Example 12
The specific experimental process and detection method are the same as example 2, except that the reaction time is 8 h, the measured product yield is 81.7%, and the selectivity is more than 99%.
Example 13
The specific experimental process and detection method are the same as example 2, except that the reaction time is 10 h, the product yield is 84.1%, and the selectivity is more than 99%.
Example 14
The specific experimental process and detection method are the same as example 2, except that the reaction time is 14 h, the product yield is 93.1%, and the selectivity is more than 99%.
Example 15
The specific experimental process and detection method are the same as example 2, except that the reaction time is 16 h, the measured product yield is 93.8%, and the selectivity is more than 99%.
Example 16
The specific experimental process and the detection method are the same as those in example 2, and only differ in that the catalyst accounts for 10 mol% of the epoxy chloropropane, the reaction time is 6 h, the reaction temperature is 50 ℃, the measured product yield is 98.8%, and the selectivity is more than 99%.
Example 17
The specific experimental process and detection method are the same as those in example 16, and the difference is only that the catalyst used is [ TMGH ] + ][ - O 2 EEPZ + ][Br - ]The product yield was found to be 98.5% with a selectivity > 99%.
Example 18
Detailed experimentsThe procedure and detection were as in example 16, except that the catalyst used was [ TMGH ] + ][ - O 2 MEPZ + ][Cl - ]The product yield was found to be 94.5% with a selectivity > 99%.
Example 19
The specific experimental process and detection method are the same as example 16, except that the molar content of the catalyst in the epichlorohydrin is 2 mol%, the measured product yield is 82.4%, and the selectivity is more than 99%.
Example 20
The specific experimental process and detection method are the same as example 16, except that the molar content of the catalyst in the epichlorohydrin is 5 mol%, the measured product yield is 92.8%, and the selectivity is more than 99%.
Example 21
The specific experimental process and detection method are the same as example 16, except that the molar content of the catalyst in the epichlorohydrin is 7 mol%, the product yield is 97.2%, and the selectivity is more than 99%.
Example 22
The specific experimental process and detection method are the same as example 16, except that the molar content of the catalyst in the epichlorohydrin is 12 mol%, the measured product yield is 99.1%, and the selectivity is more than 99%.
Example 23
The specific experimental procedure and detection method are the same as example 16, except that the reaction time is 1 h, the product yield is 81.7%, and the selectivity is more than 99%.
Example 24
The specific experimental procedure and detection method are the same as example 16, except that the reaction time is 2h, the product yield is 89.8%, and the selectivity is more than 99%.
Example 25
The specific experimental procedure and detection method are the same as example 16, except that the reaction time is 3 h, the product yield is 93.4%, and the selectivity is more than 99%.
Example 26
The specific experimental procedure and detection method are the same as those in example 16, except that the reaction time is 4 h, the product yield is 95.1% and the selectivity is more than 99%.
Example 27
The specific experimental process and detection method are the same as example 16, except that the reaction time is 5 h, the product yield is 97.6%, and the selectivity is more than 99%.
Example 28
The specific experimental process and detection method are the same as example 2, except that after the catalyst is added into the reaction kettle, 0.0225g of water is continuously added, and the product yield is 99.5% and the selectivity is more than 99%.
Example 29
The procedure and detection were as in example 28 except that the amount of water added was changed to 0.045g, the product yield was 99.1% and the selectivity was > 99%.
Example 30
The procedure and detection were as in example 28 except that the amount of added water was changed to 0.0675g, and the product yield was 98.3% and the selectivity was 99%.
Example 31
The procedure and detection were carried out in the same manner as in example 28 except that the amount of added water was changed to 0.09g, and the product yield was 98.2% and the selectivity was 99%.
Example 32
The procedure and detection were carried out in the same manner as in example 28 except that the amount of added water was changed to 0.135g, and the product yield was 97.8% and the selectivity was 98%.
Example 33
The procedure and detection were as in example 16 except that the epoxide compound used was epoxypropanol, the product yield was 49.1% and the selectivity was > 99%.
The reaction equation of the experiment is as follows:
example 34
The specific experimental procedure and detection method were the same as in example 16 except that the epoxy compound used was phenyl glycidyl ether, and the product yield was 80.8% and the selectivity was > 99%.
The reaction equation of the experiment is as follows:
example 35
The specific experimental process and detection method are the same as those in example 16, except that the epoxy compound used is styrene oxide, the reaction temperature is 60 ℃, and the CO pressure is 0.5MPa 2 The reaction time was 10 h and the product yield was found to be 96.8% with a selectivity > 99%.
The reaction equation of the experiment is as follows:
example 36
The specific experimental procedure and detection method were the same as in example 35 except that the epoxy compound used was allyl glycidyl ether phenyl glycidyl ether, and the product yield was 91.9% with a selectivity of > 99%.
The reaction equation of the experiment is as follows:
example 37
The specific experimental procedure and detection method were the same as in example 35 except that the epoxy compound used was propylene oxide, the product yield was 82.3% and the selectivity was > 99%.
Example 38
The specific experimental procedure and detection method are the same as in example 16, except that the epoxy compound used is cyclohexene oxide, the reaction temperature is 60 ℃, the reaction time is 12h, the measured product yield is 13.2%, and the selectivity is more than 99%.
The reaction equation of the experiment is as follows:
examples 39 to 46
The specific experimental process and detection method are the same as those in example 16, and the only difference is that the catalyst used is the [ TMGH ] recovered in example 16 + ][ - O 2 MEPZ + ][Br - ]The catalyst was subjected to 8 recycling experiments under the same conditions, and the results are shown in table 1. As can be seen from table 1: the recovered catalyst still has good catalytic activity.
TABLE 1 examples 39-46 catalyst recovery Using the catalytic results
Claims (10)
1. The pyrazole salt diionic liquid is characterized in that the structure of the pyrazole salt diionic liquid is as follows:
wherein n =1,X is Cl or Br;
the pyrazole salt diionic liquid is applied to the aspect of catalytic synthesis of cyclic carbonate.
2. The preparation method of the pyrazole salt diionic liquid as claimed in claim 1, which is characterized in that under the existence of an organic solvent, the carboxymethyl ethyl pyrazole salt or the carboxymethyl ethyl pyrazole salt bromide and 1,1,3,3-tetramethylguanidine are subjected to neutralization reaction under the normal temperature condition to obtain the pyrazole salt diionic liquid.
3. The method for preparing the pyrazole salt diionic liquid as claimed in claim 2, wherein the organic solvent is methanol.
4. The preparation method of the pyrazole salt diionic liquid as claimed in claim 2 or 3, wherein the molar ratio of the carboxymethyl ethyl pyrazole salt chloride or bromide to 1,1,3,3-tetramethylguanidine is 1: 1.
5. The method for catalytically synthesizing cyclic carbonate by using the pyrazole salt diionic liquid as claimed in claim 1, is characterized by comprising the following steps of:
adding the pyrazole salt diionic liquid and the epoxy compound into a reaction kettle according to the molar ratio of 2-35: 100, keeping the reaction kettle in a closed state, introducing carbon dioxide until the pressure is 0.1-0.5 MPa, carrying out cycloaddition reaction for 1-16 h at the constant temperature and the constant pressure under the condition that the temperature is 30-60 ℃, and carrying out post-treatment after the reaction is finished to obtain the cyclic carbonate.
6. The method for synthesizing cyclic carbonate by using pyrazole salt diionic liquid as claimed in claim 5, wherein a small amount of water is added to the reaction kettle to facilitate the reaction.
7. The method for catalytically synthesizing cyclic carbonate by using the diionic liquid of pyrazolate salt according to claim 5 or 6, wherein the epoxy compound has the structure
，
。
8. The method for catalytically synthesizing cyclic carbonates using a pyrazole salt diionic liquid as claimed in claim 7, wherein the molar ratio of the pyrazole salt diionic liquid to the epoxy compound is 10: 100.
9. The method for synthesizing the cyclic carbonate by using the pyrazole salt diionic liquid as the catalyst in claim 7, wherein the temperature of the cycloaddition reaction is 50 to 60 ℃, and the time of the cycloaddition reaction is 6 to 12h.
10. The method for catalytically synthesizing cyclic carbonate by using the pyrazole salt diionic liquid as claimed in claim 6, wherein the molar ratio of water to the epoxy compound is 25 to 150: 100.
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| CN108129392A (en) * | 2017-12-20 | 2018-06-08 | 河南大学 | Protonated carboxylic group glyoxaline ion liquid and the method with its catalytically synthesizing cyclic carbonate ester |
| CN109382140A (en) * | 2018-11-13 | 2019-02-26 | 河南大学 | Carboxyl-functional pyrazoles ionic liquid, synthetic method and the method with its catalytically synthesizing cyclic carbonate ester |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129392A (en) * | 2017-12-20 | 2018-06-08 | 河南大学 | Protonated carboxylic group glyoxaline ion liquid and the method with its catalytically synthesizing cyclic carbonate ester |
| CN109382140A (en) * | 2018-11-13 | 2019-02-26 | 河南大学 | Carboxyl-functional pyrazoles ionic liquid, synthetic method and the method with its catalytically synthesizing cyclic carbonate ester |
Non-Patent Citations (1)
| Title |
|---|
| Jiayin Hu et al.,.Dual-ionic liquid system: an efficient catalyst for chemical fixation of CO2 to cyclic carbonates under mild conditions.《Green Chem.》.2018,第20卷 * |
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